Alkoxylated mono alkyl glyceryl ester phosphobetaine compounds

ABSTRACT

The invention relates to a series of novel alkoxylated mono alkyl glyceryl ester phosphobetaine compounds, which are exceptional surface active agents that provide outstanding foam and are very mild to the hair and skin, in addition because of the presence of the ester linkage these materials are not persistent in the aquatic environment. This lack of persistence in the aquatic environment makes these materials greener and environmentally friendly than other non-ester containing compounds. The compounds, because they contain a pendant ionizable phosphate group and a quaternary amine compound are amphoteric surfactants that is they contain both a positive and negative charge in the same molecule. This combination of properties makes these polymers ideally suited for use in personal care applications.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates to a series of novel alkoxylated monoalkyl glyceryl ester containing phosphobetaine compounds which areexceptional surface active agents that provide outstanding foam and arevery mild to the hair and skin, and are not persistent in the aquaticenvironment. The compounds, because they contain a pendant ionizablephosphate group and a quaternary amine compound are amphotericsurfactants that is they contain both a positive and negative charge inthe same molecule. This combination of properties makes these polymersideally suited for use in personal care applications.

The compounds of the present invention are based upon raw materialswhich are prepared by the reaction of mono fatty esters of alkoxylatedglycerin reacted with a phosphating reagent followed by reaction inaqueous solution with an epoxy quat. By alkoxylated is meant reactedwith ethylene oxide or propylene oxide or combinations thereof. Theresulting compounds have a resemblance to natural occurringphospholipids and consequently are of great interest in the personalcare market.

The technology used to produce the phosphobetaine compounds of thepresent invention is very flexible and allows us to prepare performancetailored molecules for specific applications.

2. Description of the Arts and Practices

Fatty phosphobetaine compounds have been known since 1974. There areseveral patents, which have issued on this topic.

U.S. Pat. Nos. 3,856,893 and 3,928,509 both issued to Diery disclose thebasic technology used to make phosphobetaine compounds.

Later, amido and imidazoline based phosphobetaine compounds werepatented in U.S. Pat. No. 4,209,449 issued in 1980 to Mayhew andO'Lenick. This patent teaches that phosphate quats can be prepared bythe reaction of a phosphate salt, three equivalents of epichlorohydrinand in a subsequent step, three equivalents of a tertiary amine.

U.S. Pat. No. 4,215,064 issued in 1980 to Lindemann et al teaches thebasic technology that is used for the preparation of amido andimidazoline based phosphobetaine compounds. These compounds can beprepared by the reaction of a phosphate salt, one equivalent ofepichlorohydrin and one equivalent of a tertiary amine.

U.S. Pat. No. 4,243,602 issued in 1981 to O'Lenick and Mayhew teachesthe basic technology that is used for the preparation of phosphobetainecompounds based upon phosphorous acid salts. These compounds can beprepared by the reaction of a phosphorous acid salt, one equivalent ofepichlorohydrin and one equivalent of a tertiary amine.

U.S. Pat. No. 4,261,911 issued in 1981 to Lindemann et al teaches theutilization of phosphobetaine compounds based upon phosphorous acid.These compounds are useful as surfactants.

U.S. Pat. No. 4,283,542 issued in 1981 to O'Lenick and Mayhew teachesthe process technology used for the preparation of phosphobetainecompounds. These compounds can be prepared by the reaction of aphosphate salt, one equivalent of epichlorohydrin and one equivalent ofa tertiary amine.

U.S. Pat. No. 4,336,386 issued in 1982 to O'Lenick and Mayhew teachesthe technology for the preparation of imidazoline-derived phosphobetainecompounds based upon phosphorous acid salts. These compounds can beprepared by the reaction of a phosphorous acid salt, one equivalent ofepichlorohydrin and one equivalent of an imidazoline.

U.S. Pat. No. 4,503,002, which is related to U.S. Pat. No. 4,209,449issued in 1985 to Mayhew and O'Lenick teach that phosphate quats can beprepared by the reaction of a phosphate salt, three equivalents ofepichlorohydrin and three equivalents of a tertiary amine.

U.S. Pat. No. 6,180,806 issued in 2001 to O'Lenick and Imperantedisclose glyceryl phosphate quats.

Despite the fact that there was significant patenting of phosphobetainecompounds based upon phosphoric acid salts, phosphorous acids salts,tertiary amine and imidazoline, the technology needed to place a alkylor acyl moiety into the molecule and make the compounds of the presentinvention was not appreciated. It was also not until the compounds ofthe present invention that the concept and technology needed toincorporate the glyceryl group, which adds both to the improvedbiodegradation, water solubility, humectancy properties and mildness toskin and eyes.

THE INVENTION Object of the Invention

It is the object of the present invention to provide a series of novelalkoxylated glyceryl mono ester based phosphobetaine compounds which areenvironmentally friendly, high foaming, low irritation to eyes and skin,have an inverse cloud point and are substantive to the surface of afibers, and are very effective emulsifiers, and by virtue of their esterlinkage are less persistent in the aquatic environment, and are verysimilar in structure to naturally occurring phospholipids found in cellmembranes.

Still another object of the present invention is to provide a series ofalkoxylated mono alkyl glyceryl ester phosphobetaine compounds that havediffering solubilities in water and organic solvents. This is achievedby selection of the phosphate used as a raw material and the aminechosen for preparation of the phosphobetaine.

Application of the compounds of the invention can be from solvent,aqueous dispersion or solution, or applied neat in these processes.

SUMMARY OF THE INVENTION

The present invention relates to a series of novel alkoxylated monoalkyl glyceryl ester based phosphobetaine compounds. The amine grouptypically will be a quaternized nitrogen. Hence the products areamphoteric, having both an anionic and cationic group present on thesame pendant group. The glyceryl group contributes properties to thesesurfactants resulting in compounds that are outstanding emulsifiers,foaming intensely, are non irritating to eyes and skin and deposits onfiber surfaces and form effective surface modifying finishes. Thecompounds of the present invention are therefore very well suited toapplications in the personal care market.

The compounds of this invention having a pendant amphoteric group, andan ester linkage are represented by the following formula;

wherein

-   R¹ is alkyl or alkylene having between 7 and 21 carbon atoms;-   a, b and c are each independently integers ranging from 0 to 20,    with the proviso that a+b+c be equal to or greater than 1;-   R² is selected from the group consisting of;    -   alkyl having 7 to 21 carbon atoms and        R³—C(O)—N(H)—(CH₂)₃—-   R³ is alkyl having 7 to 21 carbon atoms.

The reaction sequence needed to produce the compounds of the presentinvention is multi-stepped starts with the phosphation of a alkoxylatedmono alkyl glyceryl ester compound conforming to the followingstructure;

-   -   with polyphosphoric acid        to produce:

The phosphation reagent used in the reaction is polyphosphoric acid,since the reaction with it results in minimal diester. In a preferredembodiment, the reaction is conducted at a mole ratio of 1 (ester) to0.9 phosphating reagent. This molar excess of ester results in even lessdiester.

In a subsequent step the ester phosphate is reacted with a either acompound conforming to one of the following structures;

or

to give the desired product. Both classes of products are commerciallyavailable from a variety of manufacturers including DeGussa and SiltechCorporation.

PREFERRED EMBODIMENTS

In a preferred embodiment R² alkyl having 7 to 21 carbon atoms.

In a preferred embodiment R² is R³—C(O)—N(H)—(CH₂)₃—.

In a preferred embodiment R¹ is C₇H₁₇.

In a preferred embodiment R¹ is C₉H₁₉.

In a preferred embodiment R¹ is C₁₁H₂₃.

In a preferred embodiment R¹ is C₁₃H₂₇.

In a preferred embodiment R¹ is C₁₅H₃₁.

In a preferred embodiment R¹ is C₁₇H₃₅.

In a preferred embodiment R¹ is C₁₉H₃₉.

In a preferred embodiment R¹ is C₂₁H₄₃.

In a preferred embodiment R¹ is derived from a natural oil includingcoconut, avocado, olive, castor, borage, soybean, sunflower, safflower,cottonseed, and wheat germ oil.

EXAMPLES

Alkoxylated Glyceryl Mono Esters

The alkoxylated esters used as raw materials in the preparation of theintermediate used to make the products of the present invention arearticles of commerce available from Siltech LLC Dacula, Ga. and others.They conform to the following structure;

wherein;

-   R¹ is alkyl or alkylene having between 7 and 21 carbon atoms;-   a, b and c are each independently integers ranging from 0 to 20,    with the proviso that a+b+c be equal to or greater than 1.

Example R¹ a b c 1 C₇H₁₅ 0 0 1 2 C₉H₁₉ 0 10 0 3 C₁₁H₂₃ 9 0 0 4 C₁₃H₂₇ 152 5 5 C₁₅H₃₁ 10 20 10 6 C₁₇H₃₅ 10 0 0 7 C₁₉H₃₉ 5 2 5 8 C₂₁H₄₃ 12 11 7 9C₁₇H₃₃ 5 5 5 10 C₂₁H₄₁ 20 20 20

Polyphosphoric Acid

Polyphosphoric acid is an item of commerce. It is commercially availablefrom a variety of sources. It is also called phospholeum, 115%phosphoric acid and tetraphosphoric acid. It is listed in the MerckIndex.

Preparation of Ester Phosphate

The phosphation is carried out as follows:

To a suitable vessel with good agitation is added the specified numberof grams of specified alkoxylate glyceryl mono ester (Example 1–10). Thematerial is heated to 60° C. Next, add 90.0 grams of polyphosphoricacid. The polyphosphoric acid is very thick and is added slowly toinsure a uniform mixture is achieved. After the mixture becomes uniformheat to 90.degree. C. The mixture will clear. Hold at 90° C. to 100° C.for 3 hours. The product is used without additional purification.

Alkoxylate Ester Example Example Grams 11 1 171.1 12 2 745.0 13 3 579.014 4 1208.0 15 5 2299.0 16 6 707.0 17 7 853.0 18 8 1808.0 19 9 1000.0 2010 3261.0

Reactive Intermediates (Examples 21–52)

(a) Epoxy Alkyl

The compounds of this class conform to the following structure;

wherein R² is alkyl having 7 to 21 carbon atoms.

Example R² 21 C₇H₁₇ 22 C₉H₁₉ 23 C₁₁H₂₃ 24 C₁₃H₂₇ 25 C₁₅H₃₁ 26 C₁₇H₃₅ 27C₁₉H₃₉ 28 C₂₁H₄₃

(b) Epoxy Alkylamid

The compounds of this class conform to the following structure;

wherein R² is R³—C(O)—N(H)—(CH₂)₃—and R³ is alkyl having 7 to 21 carbon atoms.

Example R² 29 C₇H₁₇ 30 C₉H₁₉ 31 C₁₁H₂₃ 32 C₁₃H₂₇ 33 C₁₅H₃₁ 34 C₁₇H₃₅ 35C₁₉H₃₉ 36 C₂₁H₄₃

(c) Chloro Alkyl

The compounds of this class conform to the following structure;

wherein R² is alkyl having 7 to 21 carbon atoms.

Example R² 37 C₇H₁₇ 38 C₉H₁₉ 39 C₁₁H₂₃ 40 C₁₃H₂₇ 41 C₁₅H₃₁ 42 C₁₇H₃₅ 43C₁₉H₃₉ 44 C₂₁H₄₃

(d) Chloro Alkylamido

The compounds of this class conform to the following structure;

wherein R² is R³—C(O)—N(H)—(CH₂)₃—and R³ is alkyl having 7 to 21 carbon atoms.

Example R² 45 C₇H₁₇ 46 C₉H₁₉ 47 C₁₁H₂₃ 48 C₁₃H₂₇ 49 C₁₅H₃₁ 50 C₁₇H₃₅ 51C₁₉H₃₉ 52 C₂₁H₄₃

Preparation of Ester Phosphobetaines

The ester phosphate (example 11–20) is reacted with the reactiveintermediate (examples 21–52) in aqueous solution at a pH of between 7and 11, with a preferred pH of 8.5–9.5 and with a preferred solids ofbetween 30–40.

General Procedure

To the specified number of grams of water is added the specified numberof grams ester phosphate (examples 11–20) under good agitation. The pHis adjusted using 50% NaOH to 8.0. The batch is heated to 80° C. Next,add the specified number of grams of the specified reactive intermediateExample (21–52). The pH is adjusted as the reaction proceeds keeping itbetween 8.0 and 9.0 with the 50% NaOH. The temperature is then keptbetween 80–90° C. and the pH is kept between 8.0 and 9.0 for about 6–8hours. The reaction progress is monitored by inorganic chlorideconcentration. The reaction is considered complete when the amount ofchloride ion reaches 98% of theoretical.

Ester phosphate Reactive Intermediate Water Example Example GramsExample Grams Grams 53 1 269.0 21 239.0 943.0 54 2 843.0 22 265.0 2058.055 3 677.0 23 293.0 1801.0 56 4 1307.0 24 321.0 3023.0 57 5 2397.0 25349.0 5100.0 58 6 805.0 26 377.0 2195.0 59 7 951.0 27 405.0 2518.0 60 81906.0 28 433.0 4344.0 61 9 1098.0 29 324.0 2640.0 62 10 3359.0 30 350.06888.0 63 1 269.0 31 378.0 1201.0 64 2 843.0 32 406.0 2319.0 65 3 677.033 434.0 2063.0 66 4 1307.0 34 462.0 3285.0 67 5 2397.0 35 490.0 5361.068 6 805.0 36 519.0 2459.0 69 7 951.0 37 276.0 2279.0 70 8 1906.0 38302.0 4100.0 71 9 1098.0 39 330.0 2652.0 72 10 3359.0 40 358.0 6903.0 731 269.0 41 386.0 1216.0 74 2 843.0 42 414.0 2334.0 75 3 677.0 43 442.02078.0 76 4 1307.0 44 470.0 3300.0 77 5 2397.0 45 361.0 5122.0 78 6805.0 46 387.0 2214.0 79 7 951.0 47 415.0 2537.0 80 8 1906.0 48 443.04362.0 81 9 1098.0 49 471.0 2914.0 82 10 3359.0 50 499.0 7165.0 83 103359.0 51 527.0 7216.0 84 9 1098.0 52 555.0 3070.0

APPLICATIONS EXAMPLES

The compounds of the present invention are used as prepared withoutadditional purification. They are high foaming compounds that give goodconditioning effects to hair and skin. Additionally, they arenon-persistent in the aquatic environment and are non-irritating to eyesand skin.

The proper selection of the compound form the present invention willresult in differing amounts of conditioning. Generally as if the R groupis small, the compounds are good wetting agents, as the R group getslonger the compounds become detergents. Finally, as they become verylarge the compounds become conditioners.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthhereinabove but rather that the claims be construed as encompassing allthe features of patentable novelty which reside in the presentinvention, including all features which would be treated as equivalentsthereof by those skilled in the art to which the invention pertains.

1. A mono alkyl glyceryl ester phosphobetaine of the followingstructure;

wherein R¹ is alkyl or alkylene having between 7 and 21 carbon atoms; a,b and c are each independently integers ranging from 0 to 20, with theproviso that a+b+c be equal to or greater than 1; R² is selected fromthe group consisting of alkyl having 7 to 21 carbon atoms andR³—C(O)—N(H)—(CH₂)₃—, R³ is alkyl having 7 to 21 carbon atoms.
 2. A monoalkyl glyceryl ester phosphobetaine of claim 1 wherein R² alkyl having 7to 21 carbon atoms.
 3. A mono alkyl glyceryl ester phosphobetaine ofclaim 1 wherein R² is R³—C(O)—N(H)—(CH₂)₃—.
 4. A mono alkyl glycerylester phosphobetaine of claim 2 wherein R¹ is C₇H₁₇.
 5. A mono alkylglyceryl ester phosphobetaine of claim 2 wherein R¹ is C₉H₁₉.
 6. A monoalkyl glyceryl ester phosphobetaine of claim 2 wherein R¹ is C₁₁H₂₃. 7.A mono alkyl glyceryl ester phosphobetaine of claim 2 wherein R¹ isC₁₃H₂₇.
 8. A mono alkyl glyceryl ester phosphobetaine of claim 2 whereinR¹ is C₁₅H₃₁.
 9. A mono alkyl glyceryl ester phosphobetaine of claim 2wherein R¹ is C₁₇H₃₅.
 10. A mono alkyl glyceryl ester phosphobetaine ofclaim 2 wherein R¹ is C₁₉H₃₉.
 11. A mono alkyl glyceryl esterphosphobetaine of claim 2 wherein R¹ is C₂₁H₄₃.
 12. A mono alkylglyceryl ester phosphobetaine of claim 3 wherein R¹ is C₇H₁₇.
 13. A monoalkyl glyceryl ester phosphobetaine of claim 3 wherein R¹ is C₉H₁₉. 14.A mono alkyl glyceryl ester phosphobetaine of claim 3 wherein R¹ isC₁₁H₂₃.
 15. A mono alkyl glyceryl ester phosphobetaine of claim 3wherein R¹ is C₁₃H₂₇.
 16. A mono alkyl glyceryl ester phosphobetaine ofclaim 3 wherein R¹ is C₁₅H₃₁.
 17. A mono alkyl glyceryl esterphosphobetaine of claim 3 wherein R¹ is C₁₇H₃₅.
 18. A mono alkylglyceryl ester phosphobetaine of claim 3 wherein R¹ is C₁₉H₃₉.
 19. Amono alkyl glyceryl ester phosphobetaine of claim 3 wherein R¹ isC₂₁H₄₃.